Modelling of polymer photodegradation for solar cell modules
The photooxidation process was modelled with input data consisting of Arrhenius parameters A (the preexponential factor) and E (the activation energy).
Somersall, A. C.↗
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Modeling of polymer photodegradation for solar cell modules
It was shown that many of the experimental observations in the photooxidation of hydrocarbon polymers can be accounted for with a computer simulation using an elementary mechanistic model with corresponding rate constants for each reaction. For outdoor applications, however, such as in photovoltaics, the variation of temperature must have important effects on the useful lifetimes of such materials. The data bank necessary to replace the isothermal rate constant values with Arrhenius activation parameters: A (the pre-exponential factor) and E (the activation energy) was searched. The best collection of data assembled to data is summarized. Note, however, that the problem is now considerably enlarged since from a theoretical point of view, with 51 of the input variables replaced with 102 parameters. The sensitivity of the overall scheme is such that even after many computer simulations, a successful photooxidation simulation with the expanded variable set was not completed. Many of the species in the complex process undergo a number of competitive pathways, the relative importance of each being often sensitive to small changes in the calculated rate constant values.
Somersall, A. C.↗
Microscopic contour changes of tribological surfaces by chemical and mechanical action
An electronic optical laser interferometer capable of resolving depth differences of as low as 30 A and planar displacements of 6000 A was constructed for the examination of surface profiles of bearing surfaces without physical contact. This instrument was used to determine topological chemical reactivity by applying a drop of dilute alcoholic hydrochloric acid and measuring the profile of the solid surface before and after application of this probe. It was found that scuffed bearing surfaces reacted much faster than virgin ones but that bearing surfaces exposed to lubricants containing an organic chloride reacted much more slowly. In a separate series of experiments, a number of stainless steel plates were heated in a nitrogen atmosphere to different temperatures and their reactivity examined later at ambient temperature. The change of surface contour as a result of the probe reaction was found to follow an Arrhenius-type relation with respect to heat treatment temperature. This result could have implications on the scuffing mechanism.
Lauer, J. L.↗
Catalytic recombination of nitrogen and oxygen on iron-cobalt-chromia spinel
The energy-transfer catalytic recombination coefficient for nitrogen and oxygen recombination on iron-cobalt-chromia spinel is inferred from stagnation-point heat flux measurements in dissociated arc-jet flow. This material was coated on several Space Shuttle Orbiter thermal protection tiles. The resulting coefficients are correlated with an Arrhenius model for convenience, and these expressions may be used to account for catalytic recombination in predictions of the heat flux on the spinel-coated tiles flown on several Space Shuttle Orbiter flights. The results are compared with those inferred by Rakich, Stewart, and Lanfranco from an Orbiter flight and arc-jet experiments. Good agreement is obtained for oxygen recombination, but agreement for nitrogen is poor.
Scott, C. D.↗
Kinetics of the reaction O + HO2 yields OH + O2 from 229 to 372 K
The discharge-flow resonance fluorescence technique has been used to obtain absolute rate data for the O + HO2 reaction from 229 to 372 K at a total pressure of 1 torr. Pseudo-first-order conditions were used with HO2 concentrations in large excess over initial atomic oxygen in order to minimize interference from secondary reactions. The results are independent of the method used to generate HO2 and atomic oxygen. At 299 K, the result is (6.1 + or - 0.4) x 10 to the -11th cu cm/molecule s. The temperature dependence expressed in Arrhenius form is (3.1 + or - 0.3) x 10 to the -11th exp/(+200 + or - 28)/T/. The error limits given are twice the standard deviation; overall experimental error is estimated to be + or - 25%.
Keyser, L. F.↗
The reaction NH2 + PH3 yields NH3 + PH2 - Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter
The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be indepenent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then contrasted with those for the corresponding reactions of H and OH with PH3.
Bosco, S. R.↗
Surface topographical changes measured by phase-locked interferometry
An electronic optical laser interferometer capable of resolving depth differences of as low as 30 A and planar displacements of 6000 A was constructed to examine surface profiles of bearing surfaces without physical contact. Topological chemical reactivity was determined by applying a drop of dilute alcoholic hydrochloric acid and measuring the profile of the solid surface before and after application of this probe. Scuffed bearing surfaces reacted much faster than virgin ones but that bearing surfaces exposed to lubricants containing an organic chloride reacted much more slowly. The reactivity of stainless steel plates, heated in a nitrogen atmosphere to different temperatures, were examined later at ambient temperature. The change of surface contour as a result of the probe reaction followed Arrhenius-type relation with respect to heat treatment temperature. The contact area of the plate of a ball/plate sliding elastohydrodynamic contact run on trimethylopropane triheptanoate with or without additives was optically profiled periodically. As scuffing was approached, the change of profile within the contact region changed much more rapidly by the acid probe and assumed a constant high value after scuffing. A nonetching metallurgical phase was found in the scuff mark, which was apparently responsible for the high reactivity.
Lauer, J. L.↗
Edge crack growth of thermally aged graphite/polyimide composites
Laminates of Celion 6000/LARC-160 and Celion 6000/PMR-15 graphite/polyimide composite materials were aged in air at temperatures of 202, 232, 260 and 288 C for various times up to 15,000 hours. Three unidirectional specimen types were studied: short beam shear (SBS), flexure, and 153 mm square panels. The interior region of the square panels exhibited little or no property degradation, whereas both laminate materials degraded and cracked preferentially at the specimen edge perpendicular to the fibers. Using a dye penetrant, the specimens were X-rayed and the crack depth measured as a function of time and temperature. A time temperature superposition of the crack data was successfully performed using an Arrhenius form for the shift factor. A direct correlation was found for edge crack depth and SBS strength for the LARC-160 laminates but the correlation for PMR-15 laminates was more complex.
Nelson, J. B.↗
The reaction NH2 + PH3 yields NH3 + PH2: Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter
The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be independent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then constrasted with those for the corresponding reactions of H and OH with PH3.
Bosco, S. R.↗
Temperature-dependent reaction-rate expression for oxygen recombination at Shuttle entry conditions
A temperature-dependent oxygen surface reaction-rate coefficient has been determined from experimental STS-2 heating and wall temperature data at altitudes of 77.91 km, 74.98 km, and 71.29 km. The coefficient is presented in an Arrhenius form and is shown to be less temperature dependent than previous results. Finite-rate viscous-shock-layer heating rates based on this present expression have been compared with predicted heating rates using the previous rate coefficients and with experimental heating data obtained over an extensive range of STS-2 and STS-3 entry conditions. A substantial improvement is obtained in comparison of experimental data and predicted heating rates using the present oxygen reaction-rate expression.
Zoby, E. V.↗
Computations and estimates of rate coefficients for hydrocarbon reactions of interest to the atmospheres of outer solar system
The rate coefficients, including Arrhenius parameters, have been computed for a number of chemical reactions involving hydrocarbon species for which experimental data are not available and which are important in planetary atmospheric models. The techniques used to calculate the kinetic parameters include the Troe and semiempirical bond energy-bond order (BEBO) or bond strength-bond length (BSBL) methods.
Laufer, A. H.↗
Kinetics of the reaction O + ClO yields Cl + O2
The bimolecular rate constant for the reaction O + ClO yields Cl + O2 has been measured over the temperature range 236-422 K in a discharge flow system using atomic oxygen resonance fluorescence at 130 nm to monitor the decay of O in an excess of ClO. The results are found to be independent of the method used to produce the ClO radical. At 296 K, the rate constant is given by (3.6 + or - 0.7) x 10 to the -11th cu cm/sec and the temperature dependence expressed in Arrhenius form by k2 = (5.0 + or - 1.0) x 10 to the -11th exp-(96 + or - 20)/T cu cm/sec. The results are compared with earlier values, and the implications for stratospheric chemistry are discussed briefly.
Leu, M.-T.↗
Gravitational effects on flames spreading over thick solid surfaces
A theoretical model for the downward spread of a flame in the gas over a semi-infinitely thick fuel bed is presented. Gas-phase chemistry is assumed to proceed at an infinite rate while the fuel bed is taken to pyrolyze at the surface in an Arrhenius fashion. Spread rates and flame shapes are computed for two different ambient oxygen concentrations for gravitational accelerations both below and above that of the earth. Predicted spread rates decrease and actual flame size increases with decreasing gravity. Results agree favorably with available, experimental results and expected results from reduced gravity experimentation.
Vedha-Nayagam, M.↗
Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene
The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.
Bosco, S. R.↗
Heat and mass transfer in combustion - Fundamental concepts and analytical techniques
Fundamental combustion phenomena and the associated flame structures in laminar gaseous flows are discussed on physical bases within the framework of the three nondimensional parameters of interest to heat and mass transfer in chemically-reacting flows, namely the Damkoehler number, the Lewis number, and the Arrhenius number which is the ratio of the reaction activation energy to the characteristic thermal energy. The model problems selected for illustration are droplet combustion, boundary layer combustion, and the propagation, flammability, and stability of premixed flames. Fundamental concepts discussed include the flame structures for large activation energy reactions, S-curve interpretation of the ignition and extinctin states, reaction-induced local-similarity and non-similarity in boundary layer flows, the origin and removal of the cold boundary difficulty in modeling flame propagation, and effects of flame stretch and preferential diffusion on flame extinction and stability. Analytical techniques introduced include the Shvab-Zeldovich formulation, the local Shvab-Zeldovich formulation, flame-sheet approximation and the associated jump formulation, and large activation energy matched asymptotic analysis. Potentially promising research areas are suggested.
Law, C. K.↗
Reliability and Engineering of Thin-Film Photovoltaic Modules. Research forum proceedings
A Research Forum on Reliability and Engineering of Thin Film Photovoltaic Modules, under sponsorship of the Jet Propulsion Laboratory's Flat Plate Solar Array (FSA) Project and the U.S. Department of Energy, was held in Washington, D.C., on March 20, 1985. Reliability attribute investigations of amorphous silicon cells, submodules, and modules were the subjects addressed by most of the Forum presentations. Included among the reliability research investigations reported were: Arrhenius-modeled accelerated stress tests on a Si cells, electrochemical corrosion, light induced effects and their potential effects on stability and reliability measurement methods, laser scribing considerations, and determination of degradation rates and mechanisms from both laboratory and outdoor exposure tests.
Ross, R. G., Jr.↗
The production of glow precursors by oxidative erosion of spacecraft surfaces
Erosion rates of organic materials are measured during a recent flight of the shuttle (STS-8). Several forms of carbon and a variety of thermosetting and thermoplastic polymers are exposed to the ram beam of atomic oxygen. Arrhenius energies of about 1000 to 2000 cal/mole were measured from the rate dependencies on temperature. If some simple assumptions are made about the chemical nature of the desorbed species, the data can be used to estimate production rates at surfaces in orbit under different conditions of temperature, oxygen atom flux, and material surface conditions.
Gregory, J. C.↗
Further explorations of cosmogonic shadow effects in the Saturnian rings
The mass distribution in the Saturnian ring system is compared with predictions from the cosmogonic theory of Alfven and Arrhenius (1975) in which matter in the rings was once a magnetized plasma, with gravitation balanced by centrifugal force and by the magnetic field. As the plasma is neutralized, the magnetic force disappears and the matter can be shown to fall in to a distance 2/3 of the original. This supports the cosmogonic shadow effect, also demonstrated for the astroidal belt and in the large scale structure of the Saturnian ring system. The relevance of the comogonic shadow effect for parts of the finer structures of the Saturnian ring system is investigated. It is shown that many structures of the present ring system can be understood as shadows and antishadows of cosmogonic origin. These appear in the form of double rings centered around a position a factor 0.64 (slightly 2/3) closer to Saturn than the causing feature.
Alfven, H.↗